Methods for producing carbon fibers from coal

ABSTRACT

A method of producing advanced carbon materials can include providing coal to a processing facility, beneficiating the coal to remove impurities from the coal, processing the beneficiated coal to produce a pitch, and treating the pitch to produce an advanced carbon material such as carbon fibers, carbon nanotubes, graphene, carbon fibers, polymers, biomaterials, or other carbon materials.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. Provisional PatentApplication No. 62/610,037 filed on 22 Dec. 2017, titled “Methods forProducing Advanced Carbon Materials from Coal,” the disclosure of whichis incorporated herein, by reference, in its entirety.

BACKGROUND

Coal is a highly varied heterogeneous material that has been mined andprincipally used for three purposes over thousands of years: 1) thegeneration of thermal heat and power generation through incineration, 2)the production of steel and other metals by coking, and 3) theproduction of what are now widely known as “petrochemicals” throughpyrolysis or liquefaction. Despite the fact that coal has beenextensively used for thousands of years, more than 99% of it has beenincinerated to produce heat and power. This process is now widely knownto produce a host of adverse environmental and economic effects.

Additional uses of coal has been the topic of research for many years.The basic chemistry of coal was well understood by at least the earlytwentieth century. Significant research was conducted with the aim ofderiving liquid transportation fuels from coal in order to supplantpetroleum. One notable breakthrough was the development of theFischer-Tropsch process in Germany, around 1925, which convertedgasified coal into liquid hydrocarbons. Additionally, Sasol, a majorSouth African company, focused on the conversion of solid coal to liquidtransportation fuels via catalytic cracking. Similarly, the UnitedStates Department of Energy sought to develop coal-based transportationfuels as an alternative to petroleum-based fuels. However, due toresearch driven petroleum technology and the decreasing costs ofpetroleum, the use of coal to produce liquid transportation fuels atlarge scales never became economically feasible.

Although significant research has been conducted on coal liquefactionand the use of coal to form other products for more than a century, theability to produce high-value, high-performance carbon based products,such as carbon fibers, from coal remains an open question. In recentyears, carbon-based technologies have come to the forefront, with rapiddevelopments being made in in the commercialization of advanced carbonmaterials such as carbon fibers, resins, graphene, and carbon nanotubes.As these advanced materials are increasingly used in mass produced, highvolume applications, there is a need to quickly and economically supplylarge quantities of advanced carbon materials to manufacturers. Thus,while improvements in the derivation of fuels and other products fromcoal are being explored, there remains significant work to be done indeveloping processes to convert coal into the advanced carbon materialsthat will be instrumental in the economy of the future.

SUMMARY

A method of producing an advanced carbon material includes providing anamount of coal to a processing facility, beneficiating the amount ofcoal at the processing facility to remove impurities therefrom,processing the beneficiated amount of coal at the processing facility toproduce an amount of pitch from at least some of the amount of coal, andtreating at least some of the amount of pitch at the processing facilityto produce the advanced carbon material.

The method of producing an advanced carbon material can includeproviding coal to a processing facility by extracting coal from a coalmine.

The method of producing an advanced carbon material can includeproviding coal to a processing facility by extracting coal from the coalmine via a high wall coal mining process.

The method of producing an advanced carbon material can includetransporting coal extracted from the coal mine to the processingfacility.

The method of producing an advanced carbon material can include usingraw coal as an initial material.

The method of producing an advanced carbon material can include heatingthe amount of coal to a first temperature for a first duration, andheating the amount of coal to a second, higher temperature for a secondduration.

The method of producing an advanced carbon material can include removingimpurities from the coal, such as mercury. Beneficiating the coal canremove at least 85% of mercury from the coal.

The method of producing an advanced carbon material can include removingwater from the coal.

The method of producing an advanced carbon material can includebeneficiating the coal to produce a beneficiated amount of coal havingless than about 5 wt. % of water.

The method of producing an advanced carbon material can include removingvolatile matter from the coal. Removal of at least 50% of the volatilematter can be removed from the coal.

The method of producing an advanced carbon material can includeprocessing the beneficiated amount of coal at the processing facility toproduce an amount of pitch from at least some of the amount of coal,including subjecting the beneficiated amount of coal to a pyrolysisprocess.

The method of producing an advanced carbon material can includeprocessing the beneficiated amount of coal at the processing facility toproduce an amount of pitch from at least some of the amount of coal,including subjecting the beneficiated amount of coal to a directliquefaction process.

The method of producing an advanced carbon material can includeprocessing the beneficiated amount of coal at the processing facilityincludes subjecting the beneficiated amount of coal to an indirectliquefaction process.

The method of producing an advanced carbon material can includeprocessing the beneficiated amount of coal at the processing facilityincludes producing an amount of solid char.

The method of producing an advanced carbon material can include treatingat least some solid char to produce an amount of activated carbon.

The method of producing an advanced carbon material can includeprocessing the beneficiated amount of coal at the processing facilityincludes producing an amount of coal liquid extract.

The method of producing an advanced carbon material can include treatingat least some of the coal liquid extract to produce an amount ofbenzene.

The method of producing an advanced carbon material can include treatingat least some of the coal liquid extract to produce an amount ofparaxylene.

The method of producing an advanced carbon material can include usingpitch that comprises one of mesophase pitch, isotropic pitch, ormesophase pitch.

The method of producing an advanced carbon material can include spinningat least some of the amount of pitch to produce the advanced carbonmaterial.

The method of producing an advanced carbon material can include formingadvanced carbon materials including one or more of carbon fibers, carbonnanotubes, graphite, graphene, graphite nano-platelets, fullerenes,pyrolytic carbon, carbon foams, and resins.

The method of producing an advanced carbon material can include treatingat least some of the amount of pitch at the processing facilityincluding treating a first amount of pitch to form a first advancedcarbon material and treating a second amount of pitch to form a secondadvanced carbon material.

The method of producing an advanced carbon material wherein the firstadvanced carbon material includes carbon fibers and the second advancedcarbon material includes a polymer.

The method of producing an advanced carbon material can includecombining the carbon fibers and the polymer to form a carbon fiberreinforced polymer.

According to some embodiments, a method of producing synthetic graphitefrom coal at a processing facility, can comprise providing coal to theprocessing facility, beneficiating the coal to remove a desired amountof impurities therefrom, and processing the beneficiated coal to producesynthetic graphite.

The synthetic graphite includes a desired amount of impurities. Theimpurities can include one or more of cadmium, selenium, or othermetals. The method can further comprise processing the syntheticgraphite to produce synthetic graphene. Processing the syntheticgraphite to produce synthetic graphene can comprise exfoliation. Thesynthetic graphene can include a desired amount of impurities.

According to some embodiments, a synthetic graphite formed from pitchderived from coal is described herein. The synthetic graphite canfurther comprise a desired amount of one or more impurities found incoal.

According to some embodiments, a synthetic graphene formed from pitchderived from coal is described herein. The synthetic graphene canfurther comprise a desired amount of one or more impurities found incoal.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings illustrate various embodiments of the presentapparatus and are a part of the specification. The illustratedembodiments are merely examples of the present apparatus and do notlimit the scope thereof.

FIG. 1 is a flow chart of an example method 100 to form carbon fibers,according to an embodiment.

FIG. 2 is a flow chart of an example method 200 to form carbon fibersusing a direct liquefaction process, according to an embodiment.

FIG. 3 is a flow chart of an example method 300 to form carbon fibersusing an indirect liquefaction process, according to an embodiment.

FIG. 4 is a flow chart of an example method 400 to form carbon fibersusing one or more membranes, according to an embodiment.

FIG. 5 illustrates a material flow diagram of an example of a method 500of producing carbon fiber and, optionally, one or more advanced carbonmaterials from coal in accordance with the present disclosure, accordingto an embodiment.

FIG. 6 is a diagram illustrating the flow of energy and coal in aprocessing facility for the production of one or more advanced carbonmaterials as described herein and according to some embodiments.

FIG. 7 is a diagram illustrating the process flow of raw coal, forexample from a high wall coal mine, as it is processed according to theembodiments described herein to form various advanced carbon materials,such as activated carbon, graphene, materials for use in batteries, andbuilding and construction materials, according to an embodiment.

FIG. 8 is a diagram illustrating the process flow of raw coal to variousadvanced carbon materials according to the processes described herein,according to an embodiment.

Throughout the drawings, identical reference numbers designate similar,but not necessarily identical, elements.

DETAILED DESCRIPTION

As described below, carbon fibers can be produced from raw, mined coal.In an embodiment, raw coal can be transported to a processing facility.The coal can then be beneficiated in order to remove a desired amount ofimpurities. The impurities (e.g., any compound or element other thancarbon or hydrogen) removed from the coal can include at least one ofmercury, arsenic, cadmium, other heavy metals, water, or volatilecompounds. In some cases, beneficiation can include heating the coal toremove these impurities. The beneficiated coal can then be processed toproduce pitch and, optionally, one or more additional advanced carbonmaterials (i.e., non-carbon fiber advanced carbon materials). Theprocessing can include subjecting the beneficiated coal to a liquidextraction process (e.g., pyrolysis process, direct liquefactionprocess, indirect liquefaction process, or processing involving one ormore membranes). In some cases, these processes disclosed herein canproduce one or more byproducts (e.g., at least one of gases, solid char,or coal liquid extract) in addition to pitch which themselves can beprocessed to form useful materials, such as carbon fiber and additionaladvanced carbon materials. For example, solid char can be processed toform activated carbon, and coal liquid extracted can be processed toform aromatic compounds such as benzene and paraxylene.

In some embodiments, the pitch produced by the processes describedherein can be an isotropic pitch, and can be converted to a mesophasepitch by processing as needed or desired. The pitch can then be treatedand/or modified to produce the carbon fiber (e.g., the pitch can be spunto form carbon fibers), and, optionally, one or more additional advancedcarbon materials (e.g., processed to form synthetic graphite, etc.). Thecarbon fiber and, optionally, the additional advanced carbon materialscan be subjected to further processing, or can be delivered to thirdparties for use, for example in manufacturing. In some cases, the carbonfiber can be produced and combined to form secondary material, such as aresin or polymer to form a carbon fiber reinforced composite.

In some embodiments, one or more of the processes or process stepsdescribed herein can utilize or be carried out in the presence of one ormore catalysts. For example, one or more process can include ahydrogenation catalyst. In some embodiments, the catalyst can comprise ametal (e.g., platinum). In some cases, the catalyst can be a multi-partcatalyst (e.g., a catalyst comprising two or more metals). In somecases, a catalyst can include a ceramic or mineral material (e.g., asilicate material, such as an aluminosilicate material). In some cases,a catalyst can include any catalytic material now known or as can yet bediscovered for use in processing coal.

In some embodiments, all of the beneficiation, processing, and treatmentsteps described herein can be performed at a single processing facility,for example a single processing plant or compound. However, in otherembodiments, one or more steps can be performed at separate facilitiesand the products of each step can be stored and transported between eachfacility. As used herein, the term processing facility can refer to oneor more laboratories, buildings, process flows, or other apparatuses atabout the same geographic location. For example, a processing facilitycan comprise a single building or factory complex at a single geographiclocation which comprises such equipment to perform the processes andmethods described herein.

In an embodiment, carbon fiber is the only advanced carbon materialproduced during the processes disclosed herein. In an embodiment, aspreviously discussed, the processes disclosed herein can form carbonfiber and one or more additional advanced carbon materials. In anexample, the one or more additional advanced carbon materials caninclude, but are not limited to, resins (e.g., polyacrylonitrile,polyurethane resins, cyanate ester resins, epoxy resins, methacrylateresins, polyester resins, and other suitable resins), carbon foams,single-walled carbon nanotubes, multi-walled carbon nanotubes, carbonmegatubes, graphite, graphene, graphite nano-platelets, nanoribbons,nanobuds, fullerenes (e.g., buckminsterfullerene and multi-coredfullerenes), quantum dots, activated carbon, and pyrolyzed carbon. In anexample, the additional advanced carbon materials produced by theprocesses described herein can also include, but are not limited topolymers. In an example, the additional advanced carbon materialsproduced by the processes described herein can also include one or morematerials that can be used as precursors in the formation of additionaladvanced carbon materials. Examples of the precursors can include atleast one of alkanes, alkenes, or alkynes. In an example, the additionaladvanced carbon materials can comprise biologically useful materials orbiopolymers (e.g., at least one of proteins, amino acids, nucleic acids,collagen, chitosan, or sugars).

Producing the carbon fiber and, optionally, the one or more additionaladvanced carbon materials from coal has several advantages overproducing the carbon fiber and, optionally, the one or more additionaladvanced carbon materials from other carbon sources (e.g., oil). Forexample, the supply and price of oil is highly volatile which can affectthe ability of manufacturers to obtain oil for the production of thecarbon fibers and the additional advanced carbon materials. This, inturn, can cause shortages of the carbon fibers and the additionaladvanced carbon materials which can hamper manufacturer's ability tomake devices, parts, etc. that include the carbon fiber and theadditional advanced carbon materials. Additionally, producing the resinfrom coal produces at least one of resin, pitch, or one or morebyproducts exhibiting a low hydrogen to carbon ratio (e.g., a hydrogento carbon ratio of less than about 0.5, less than about 0.2, or lessthan about 0.1). The low hydrogen to carbon ratio can at least oneimprove the yield of resin formed from the coal, eliminate the need foran external source of hydrogen, or reduce the amount of carbon dioxideproduced during the processes disclosed herein. Further, coal caninclude one or more impurities therein. The presence of the one or moreimpurities can affect the properties of the carbon fiber and theadditional advanced carbon material. For instance, at least some of atleast one of the impurities can intentionally and selectively not beremoved from the coal during the beneficiation process or during anotherprocess. The impurity or impurities that are not removed from the coalcan act as dopants in the carbon fiber and the one or more additionaladvance carbon materials which, in turn, can affect the properties ofthe carbon fiber and the one or more additional advanced carbonmaterials. As such, the impurities that are present in the coal and theability to selectively remove the impurities from the coal can allow fora high degree of control over the composition and properties of thecarbon fiber and the additional advanced carbon materials that aremanufactured from coal. Further, the presence of the impurities in thecoal result in less processing being required to form the carbon fiberand the additional advanced carbon materials. For example, themaintaining the impurity or impurities in the coal can at least one ofsimplify the beneficiation processes or other purification processes,facilitate the operation of one or more other non-beneficiationprocesses, or preclude the need for actively doping the coal, carbonfiber, or additional advanced carbon materials. Additionally, the carbonfibers formed from coal can exhibit higher graphene levels, are moreelastic, and exhibit higher tensile strengths than carbon fiber formedfrom oil.

Methods of Forming the Carbon Fiber and Other Byproducts from Raw Coal

FIG. 1 is a flow chart of an example method 100 to form carbon fibers,according to an embodiment. The method 100 can include one or more ofproviding raw coal to a processing facility at block 110; beneficiatingthe raw coal via the processing facility at block 120 to remove adesired amount of water, metals, and/or other impurities from the coal;pyrolyzing at least some of the beneficiated coal via the processingfacility at block 130; producing pitch at block 140; and modifying atleast some of the pitch to produce carbon fibers at block 150. Thecarbon fibers can include a selected amount of a remainder of one ormore impurities that were not removed during the method 100. The method100 is only an example. As such, one or more blocks of the method 100can be omitted, supplemented, combined, or divided. Further, the method100 can include one or more additional acts, such as producing at leastone byproduct from the coal (e.g., at least one of char, one or moregases, or one or more coal liquid extracts) or treating the pitch toproduce one or more additional advanced carbon materials.

In some embodiments, the raw coal can be provided to a processingfacility at block 110 by any method that is now known or that can bedeveloped in the future. For example, coal is generally extracted fromnaturally occurring layers or veins, known as coal beds or coal seams,by mining. Coal can be extracted by surface mining, underground mining,or various other forms of mining. Typically, coal that has beenextracted via mining, but has not been otherwise processed is referredto as raw coal. In some cases, the raw coal can be extracted via asurface mining process, such as a high wall mining process, strip miningprocess, or contour mining process. In some cases, the raw coal can beextracted via an underground mining process, such as by a longwallmining process, continuous mining process, blast mining process, retreatmining process, or room and pillar mining process.

The raw coal can be mined or extracted from a location relatively nearto the processing facility. For example, the processing facility can belocated at, or near a coal extraction area. However, in other cases coalcan be extracted from any location and transported to the processingfacility. In some cases raw coal can be provided to the processingfacility as needed to produce a desired amount of advanced carbonmaterials. However, in some other cases, raw coal can be provided andstored at the processing facility until it is processed.

The coal provided in block 110 can be ranked or graded based on itscontents and properties. Although a variety of coal classificationschemes exist, a general metamorphic grade is used herein to generallydescribe raw coal. These grades are used generally to aid in theunderstanding of the present disclosure and are not intended to limit totypes of coal which can be used to produce the carbon fiber and,optionally, the one or more additional advanced carbon materials asdescribed herein. While certain classifications of coal can bepreferable for use in the processes described herein, such processes arenot strictly limited to the discussed classifications of coal, if any.In some embodiments, the coal utilized by the processes described hereincan be lignite coal, and can have a volatile content of greater thanabout 45 wt. %. In some embodiments, the coal can be sub-bituminouscoal, bituminous coal, and/or anthracite coal. In some embodiments, thecoal can be coal extracted from the Brook Mine near Sheridan, Wyo. It iscurrently believed by the inventors that the composition of the coalextracted from the Brook Mine includes several impurities at beneficialconcentrations that can facilitate the formation of carbon fiberexhibiting certain mechanical, chemical, and/or electrical properties,as discussed in more detail below. In some cases, the preferred coal foruse in the processes described herein can be selected by the skilledartisan. For example, the preferred coal can be selected based one atleast one of one or more destructive or non-destructive chemicalanalyzation techniques (e.g., Raman spectroscopy, energy dispersivex-ray spectroscopy, etc.) or one or more computing techniques. In someembodiments, the coal can exhibit an initial hydrogen to carbon ratiothat is greater than about 0.7, such as in ranges 0.7 to about 1.0,about 0.7 to about 0.75, about 0.725 to about 0.0775, about 0.75 toabout 0.8, about 0.0775 to about 0.85, about 0.8 to about 0.9, about0.85 to about 0.95, or about 0.9 to about 1.0.

As previously discussed, the raw coal can be provided to a processingfacility at block 110 for use in the method 100. The processing facilitycan have the capacity to store raw coal for use as needed, or canreceive raw coal as needed to produce a desired amount of the carbonfiber. As is well known in the art, coal can be provided via truck,train, or any other form of transportation. Further, the processingfacility can be situated at a coal extraction site, such that coalextraction site can be considered as part of the processing facility.

As previously discussed, the raw coal can include one or more impuritiestherein. The one or more impurities can include, but are not limited tovolatile heavy metals (e.g., mercury, selenium, arsenic, and cadmium),alkali metals (e.g., sodium metals, potassium metals), heteroatoms(e.g., sulfur, oxygen, and halogens), silicon, aluminum, titanium,calcium, iron, magnesium, sodium, potassium, sulfur, strontium, barium,manganese, phosphorus, antimony, arsenic, barium, beryllium, boron,bromine, cadmium, chlorine, chromium, cobalt, copper, fluorine, lead,lithium, manganese, mercury, molybdenum, nickel, selenium, silver,strontium, thallium, tin, vanadium, zinc, and/or zirconium or oxidesthereof. For example, depending on the impurity and the source of theraw coal, any of the impurities disclosed herein can form 0 weightpercent (“wt. %”) to about 25 wt. % of the raw coal, such as in rangesof about greater than 0 wt. % to about 0.001 wt. %, about 0.0005 wt. %to about 0.002 wt. %, about 0.001 wt. % to about 0.003 wt. %, about0.002 wt. % to about 0.004 wt. %, about 0.003 wt. % to about 0.005 wt.%, about 0.004 wt. % to about 0.006 wt. %, about 0.005 wt. % to about0.008 wt. %, about 0.007 wt. to about 0.01 wt. %, about 0.009 wt. % toabout 0.02 wt. %, about 0.01 wt. % to about 0.03 wt. %, about 0.02 wt. %to about 0.04 wt. %, about 0.03 wt. % to about 0.05 wt. %, about 0.04wt. % to about 0.06 wt. %, about 0.05 wt. % to about 0.08 wt. %, about0.07 wt. % to about 0.1 wt. %, about 0.09 wt. % to about 0.2 wt. %,about 0.1 wt. % to about 0.3 wt. %, about 0.2 wt. % to about 0.4 wt. %,about 0.3 wt. % to about 0.5 wt. %, about 0.4 wt. % to about 0.6 wt. %,about 0.5 wt. % to about 0.8 wt. %, about 0.7 wt. % to about 1 wt. %,about 0.9 wt. % to about 2 wt. %, about 1 wt. % to about 4 wt. %, about3 wt. % to about 6 wt. %, about 5 wt. % to about 8 wt. %, about 7 wt. %to about 10 wt. %, about 9 wt. % to about 15 wt. %, or about 10 wt. % toabout 25 wt. %.

At block 120, the raw coal can be beneficiated to remove at least someof at least one of the impurities that are present in the raw coal toform beneficiated coal (also known as upgraded coal), according to anembodiment. For example, the raw coal can be beneficiated to remove atleast one water, heavy metals, volatile compounds, alkali metals, orheteroatoms from the raw coal, thereby producing the beneficiated coal.In an embodiment, the raw coal can be beneficiated to remove asignificant portion of at least one of the impurities.

The beneficiation process can include heating the raw coal to one ormore desired temperatures. The one or more desired temperature can beabout 100° C. to about 500° C., such as in ranges of about 100° C. toabout 290° C., 100° C. to about 150° C., about 125° C. to about 200° C.,or about 150° C. to about 290° C. The temperature that the raw coal isheated to can be selected to selectively remove at least some of atleast one of the impurities that are present in the raw coal. Forexample, the raw coal can be heated to a temperature of about 100° C. toabout 150° C. to remove moisture from the raw coal and about 150° C. toabout 290° C. to remove volatile metals from the raw coal. In somecases, the beneficiation process can comprise heating the raw coal to afirst desired temperature. Heating the raw coal to the first desiredtemperature can remove one or more first impurities. In someembodiments, beneficiation can then include heating the raw coal to asecond, higher desired temperature. Heating the raw coal to the seconddesired temperature can remove one or more second impurities.

The beneficiation process can include heating the raw coal to thedesired temperature for a desired duration. The desired duration can beabout 1 second to several days, such as in ranges of about 1 second toabout 1 minute, about 30 seconds to about 30 minutes, about 1 minute toabout 1 hour, about 30 minutes to about 3 hours, about 1 hours to about5 hours, about 3 hours to about 10 hours, about 7 hours to about 18hours, about 12 hours to about 1 day, or about 18 hours to about 3 days.Typically, increasing the duration that the raw coal is heated to thedesired temperature can increase the amount of the one or moreimpurities are removed from the raw coal. However, the raw coal canexhibit a maximum duration where heating the raw coal for periods oftime longer than the maximum duration will have little or no effect onthe amount of the one or more impurities that are removed from the rawcoal. In some cases, the beneficiation process can comprise heating theraw coal to a first desired temperature for a first duration followed byheating the raw coal to a second, higher desired temperature for asecond duration. The first and second durations can be the same ordifferent.

In an embodiment, the beneficiation process can include heating the rawcoal in an atmosphere comprising a halogen gas which can facilitateremoval of one or more of the impurities from the raw coal and preventoxidation or other reactions with the raw coal. In some embodiments, thecoal can be beneficiated by heating the raw coal in an atmosphereincluding hydrogen which can increase the hydrogen to carbon ratio. Insuch an embodiment, the hydrogen can be provided from an outsidehydrogen source or from hydrogen that was collected in another stage ofthe method 100. In some embodiments, the coal can be beneficiated byheating the raw coal in an atmosphere that is substantially hydrogenfree. In such an embodiment, the substantially hydrogen free atmospherecan decrease the hydrogen to carbon ratio.

In some embodiments, the coal can be beneficiated by heating the rawcoal in an atmosphere including hydrogen which can increase the hydrogento carbon ratio. In such an embodiment, the hydrogen can be providedfrom an outside hydrogen source or from hydrogen that was collected inanother stage of the method 100. In some embodiments, the coal can bebeneficiated by heating the raw coal in an atmosphere that issubstantially hydrogen free. In such an embodiment, the substantiallyhydrogen free atmosphere can decrease the hydrogen to carbon ratio.

In some other embodiments, the coal can be beneficiated by heating thecoal to a desired temperature in the presence of one or more catalystcompounds. In some cases, beneficiating the coal can comprise pyrolyzingthe coal, for example in the presence of a catalyst. In someembodiments, the raw coal can be beneficiated at or near atmosphericpressure (e.g., 0.8 to about 1.2 atmospheres), though the raw coal canbe beneficiated at higher or lower pressures.

In some embodiments, beneficiation can include subjecting the raw coalto a WRITECoal beneficiation process, as described, for example, in U.S.Pat. No. 9,181,509 which is hereby incorporate by reference in itsentirety. In some other embodiments, the coal can be beneficiated byheating the coal to a desired temperature in the presence of one or morecatalyst compounds. In some cases, beneficiating the coal can comprisepyrolyzing the coal, for example in the presence of a catalyst. In somecases, the coal can be beneficiated by the BenePlus System, as developedand licensed by LP Amina and as described, for example, in U.S. PatentPublication No. 2017/0198221 which is hereby incorporated by referencein its entirety.

The beneficiated coal can comprise a significantly reduced amount (e.g.,at least 25 wt. %, at least 50 wt. %, at least 75 wt. %, at least 90 wt.%, at least 95 wt. %, or at least 99 wt. %) of at least one of mercury,cadmium, other heavy metals, water, any of the other impuritiesdisclosed herein, or any other impurity that can be present in the rawcoal. The amount of the impurities that are left in the beneficiatedcoal can depend on the temperature that the raw coal was heated, theduration that the raw coal was heated, the atmosphere that the raw coalwas exposed to during the beneficiation process, the presence ofcatalysts, etc. For example, beneficiating the coal can reduce theamount of mercury in the coal by about at least about 70 wt. %, 75 wt.%, 80 wt. %, 85 wt. %, 90 wt. %, or 92 wt. % or more. In some cases,beneficiating the coal can reduce the water or moisture content of thecoal to less than about 5 wt. %, 4 wt. %, 3 wt. %, 2 wt. %, or 1.5 wt. %or lower. In some cases, beneficiating the coal can remove one or moreof hydrogen, sulfur, oxygen, arsenic, selenium, cadmium, or volatilematter from the coal. The amount of one or more of these elements in thecoal can be reduced by about 25 wt. % to about 90 wt. %.

However, as previously discussed, it can be desirable for a desiredamount of one or more impurities to remain in the beneficiated coalafter being subjected to a beneficiation process. For example, thebeneficiation process can remove a desired amount of impurities suchthat a predetermined amount of mercury, cadmium, selenium, alkalimetals, heterogeneous elements, and/or another element can selectivelyremain in the beneficiated coal after processing. In some cases, thedesired amount of impurity that can remain in the beneficiated coal canbe useful in the subsequent formation of the carbon fiber or,optionally, the one or more additional advanced carbon materials. Insome cases, the desired amount of the impurity that can remain in thebeneficiated coal can be incorporated into the carbon fiber and,optionally, the one or more advanced carbon materials. For example,where the advanced carbon material comprises synthetic graphene, adesired amount of cadmium can remain in the beneficiated coal and can beincorporated into the synthetic graphene to thereby improve theelectrical, mechanical, or chemical properties thereof.

In an embodiment, the beneficiation process can be configured tomaintain at least some of any of the impurities disclosed herein at anyof the concentrations disclosed herein in the beneficiated coal afterblock 120 (but before block 130).

In an embodiment, the beneficiation process can be configured todecrease the hydrogen to carbon ratio of the coal. For example, afterthe beneficiation process, the hydrogen to carbon ratio of beneficiatedcoal can less than about 0.8, such as in ranges of about 0.6 to about0.7, about 0.65 to about 0.75, or about 0.7 to about 0.8.

In some embodiments, beneficiating the coal during act 120 can produceone or more byproducts, such as one or more byproducts that can becaptured and used in later processing steps, that can be valuable in andof themselves, or that can be subjected to further processing or use inthe method 100. For example, beneficiating the coal can produce orseparate gases or coal liquid extracts from the raw coal. These gasesand/or coal liquid extracts can be captured or separated duringprocessing. For example, beneficiating the coal at block 120 can produceat least one of H₂, CO₂, CO, CH₄, C₂H₄, C₃H₆, or other hydrocarbongases, which can be captured and subsequently utilized in block 130 orin other process steps. In some cases, beneficiating the coal can resultin coal liquid extracts (e.g., toluene or benzene) which can be capturedfor subsequent use or processing. In some cases, the impurities removedfrom the coal by the beneficiation process at block 120 can be capturedfor subsequent use. For example, water removed from the coal by thebeneficiation process can be capture and utilized in subsequent processsteps. In some embodiments, beneficiating the coal can also produce asolid material known as ash or char. In some cases, this char can besubjected to further processing to form activated carbon.

At block 130 the beneficiated coal can be processed via the processingfacility. In some embodiments, processing the beneficiated coal caninclude subjecting the beneficiated coal to a liquid extraction process,such as a pyrolysis process (e.g., a high temperature pyrolysis processor a mild temperature pyrolysis process). It is noted that otherliquefaction processes can be used instead of or in conjunction with thepyrolysis process, such as using a direct liquefaction process(discussed in more detail with regard to FIG. 2), an indirectliquefaction process (discussed in more detail with regard to FIG. 3),membranes (e.g., discussed in more detail with regard to FIG. 4), anelectric arc process, a super critical solvent extraction process, or anelectromagnetic heating process. The liquid extraction process canconvert the beneficiated coal into at least one of pitch, one or moregases, one or more coal liquid extracts, or char.

In an embodiment, the liquid extraction processes of block 130 cancomprise pyrolyzing the beneficiated coal via the processing facility.Pyrolyzing the beneficiated coal to form carbon fibers can includeheating the beneficiated coal to a desired temperature for a desiredduration, with or without elevating the pressure applied to thebeneficiated coal. At the elevated temperatures, some of the organicstructures within the beneficiated coal begin to breakdown forming lowermolecular weight pyrolytic fragments. Some of the lower molecular weightpyrolytic fragments can escape the beneficiated coal as light gases(e.g., hydrogen, methane, carbon dioxide, etc.). These light gases canbe captured and/or reused as discussed in more detail below. However,some of the lower molecular weight pyrolytic fragments can recombine ordepolymerize to form small ring aromatic structures (e.g., single ringaromatic structure). The small ring aromatic structure can undergocondensation reactions wherein the small aromatic ring structure jointogether to form larger ring aromatic structures (e.g., polyaromatichydrocarbons). Examples of the condensation reactions includes at leastone of ring condensation, ring fusion, dehydrogenation, or othercondensation reactions that grow the small ring aromatic structure. Thelarger ring aromatic structures can comprise isotropic pitches,isotropic resins, other products that include aligned polyaromaticlayers, liquid crystalline structure (e.g. anisotropic pitches oranisotropic resins), mesophase pitches, or mesophase resins.

In an example, pyrolyzing the beneficiated coal can comprise a hightemperature pyrolysis process that includes heating the beneficiatedcoal to a temperature greater than about 1000° C. at atmosphericprocess. The high temperature pyrolysis process can form benzenecompounds, phenol compounds, high value oil, or other compounds that areuseful in the formation of carbon fibers. In an example, pyrolyzing thebeneficiated coal can comprise a mild temperature pyrolysis process thatincludes heating the beneficiated coal to a temperature of about 400° C.to about 650° C. at atmospheric pressure. The mild temperature pyrolysisprocess is likely to form coke than the high temperature pyrolysisprocess which can facilitate the formation of the resins disclosedherein. In some cases, the coal can be heated at high pressure (e.g., apressure greater than about 1 atmosphere) and in the presence of asolvent. For example, the beneficiated coal can be pyrolyzed in thepresence of a CO₂ solvent which can be held in a supercritical state. Insome cases, the beneficiated coal can be pyrolyzed in a hydrogenatmosphere (e.g., hydrogen provided from an outside hydrogen source orhydrogen collected during the method 100) to increase the hydrogen tocarbon ratio of the beneficiated coal or pyrolyzed in a hydrogen freeatmosphere to decrease the hydrogen to carbon ratio of the beneficiatedcoal. In an embodiment, the beneficiated coal can be pyrolyzed in ahydrogen atmosphere (e.g., hydrogen provided from an outside hydrogensource or hydrogen collected from another stop of the method 100) toincrease the hydrogen to carbon ratio of the coal or pyrolyzed in ahydrogen free atmosphere to decrease the hydrogen to carbon ratio of thecoal. In some cases, the beneficiated coal can be pyrolyzed by the MuSCLSystem developed by TerraPower described, for example, in U.S. Pat. No.10,144,874 which is hereby incorporate by reference in its entirety.Additional examples of pyrolysis processes that can be used to processthe beneficiated coal are described in U.S. Patent ApplicationPublication No. 2017/0198221, U.S. Patent Application Publication No.2018/0311657, and The ENCOAL mild gasification project, a DOEAssessment, DOE/NETL-2002/1171 (2002), the disclosure of each of whichis incorporated herein, in its entirety, by this reference.

In some embodiments, the pyrolysis process can comprise exposing thebeneficiated coal to electromagnetic radiation at a desired intensityand for a desired duration. For example, block 130 can comprise exposingthe beneficiated coal to microwave and/or radiofrequency (RF) radiationfor a desired duration as part of the pyrolysis process. In some cases,this pyrolysis process can result in the bulk of the beneficiated coalremaining below pyrolytic temperatures, while individual particles ofcoal can be subjected to temperatures greater than about 1200° F. Insome cases, this pyrolysis process can also comprise methane activationand/or methylation of at least some of the carbon comprising thebeneficiated coal. In some embodiments, the beneficiated coal can bepyrolyzed by the Wave Liquefaction process developed by H QuestVanguard, Inc. as described, for example, in U.S. Patent Publication No.2017/0080399 which is hereby incorporate by reference in its entirety.Additional examples of processes for processing coal by exposing thebeneficiated coal to electromagnetic radiation are disclosed in U.S.Pat. No. 6,512,216 and U.S. Patent Application Publication No.2017/0101584, the disclosures of each of which is incorporated herein,in its entirety, by this references. Further examples of processes forprocessing coal by exposing the beneficiated coal to electromagneticradiation are disclosed in U.S. Patent Application Publication No.2018/0311657, the disclosure of which was previously incorporatedherein.

Block 130 can be configured to prevent or selectively maintain selectedquantities of the one or more impurities in the pyrolyzed coal. Forexample, after block 130, the pitch can include any of the impuritiesdisclosed herein at any of the concentrations disclosed herein.

In an embodiment, after block 130, the pyrolyzed can exhibit a hydrogento carbon ratio of less than about 0.8, such as in ranges as less thanabout 0.1, less than about 0.2, about 0.1 to about 0.2, about 0.15 toabout 0.25, about 0.2 to about 0.4, about 0.3 to about 0.5, about 0.4 toabout 0.6, or about 0.5 to about 0.7.

At block 140, pitch and, optionally, one or more byproducts (e.g., atleast one of one or more gases, one or more coal liquid extracts, orchar) are processed (e.g., extracted to the pyrolyzed coal) via theprocessing facility. In an embodiment, block 140 can represent theresult of at least one of block 120 or block 130, rather than a separateaction or process step. In an embodiment, block 140 can be performedsubstantially simultaneously with at least one of block 120 or block130. In an embodiment, block 140 can be performed after at least one ofblock 120 or block 130.

In an embodiment, block 140 can include adding one or more additives tothe beneficiated coal. For example, one or more other gases or liquidscan be used during block 140 to add one or more additives to thebeneficiated coal. Examples of gases or liquids that can be used duringblock 104 include hydrogen containing gases, natural gases, CO₂,petroleum products, one or more materials or compounds that are producedduring at least one of block 120 or block 130, or one or more materialsor compounds that can be produced by or captured during previousiterations of method 100.

As previously discussed, the raw coal can include one or more impuritiestherein and blocks 120 and 130 can be configured to not remove at leastsome of the impurities such that the beneficiated or pyrolyzed coalincludes at least some of the impurities. The presence of the one ormore impurities in the beneficiated or pyrolyzed coal can make addingone or more additives to the beneficiated or pyrolyzed coal unnecessaryor can reduce the amount of additives that are added to the beneficiatedor pyrolyzed coal. As such, the presence of the one or more impuritiesin the beneficiated or pyrolyzed coal can make the method 100 moreefficient than methods of forming carbon fibers from a non-coal sourcesince the beneficiated or pyrolyzed coal can have less additives addedthereto than the non-coal source.

In some embodiments, pitch can be produced via the processing facilityat block 140. As used herein, pitch, also known as coal pitch, coal tar,or coal tar pitch, can refer to a mixture of one or more typicallyviscoelastic polymers as will be well understood by the skilled artisan.In some embodiments, the pitch produced at block 140 can be a directresult of processing the beneficiated coal at step 130. The pitchproduced at block 140 can comprise one or more high molecular weightpolymers. In some embodiments, the pitch can have a melting point ofgreater than about 650° F. In some embodiments, the pitch can have amelting point that is high enough that some of the pitch (e.g., portionsof the pitch not used to form the carbon fiber) can be used in a carbonfiber spinning process without the need for a plasticizer.

In an embodiment, the pitch can comprise aromatic hydrocarbons, forexample polycyclic aromatic hydrocarbons. In some cases, the pitch cancomprise at least about 50 wt. % polycyclic aromatic hydrocarbons, atleast about 60 wt. %, 70 wt. %, 80 wt. %, 90 wt. %, 95 wt. %, or 99 wt.% or greater of polycyclic aromatic hydrocarbons. In an embodiment, thepitch can comprise less than about 0.1 wt. % ash or other solidmaterial, less than about 0.05 wt. % ash or solid material, or less thanabout 0.01 wt. % ash or solid material. In some cases, the pitch canhave a flash point greater than about 230° F., greater than about 250°F., greater than about 300° F., or in ranges of about 230° F. to about250° F., about 240° F. to about 275° F., about 250° F. to about 300° F.,about 275° F. to about 350° F., or about 300° F. to about 400° F. Insome cases, the pitch can have an API gravity of less than about 4, lessthan about 3, or less than about 2, or less than about 1.5. In someembodiments, the pitch produced by the method 100 is not coke pitch.That is, in some cases, the pitch produced at block 140 is not producedfrom coke or a coke-based material. In some embodiments, coke is notproduced at any point during the method 100.

In some embodiments, the pitch can include any of the impuritiesdisclosed herein at any of the concentrations disclosed herein.

In some embodiments, the pitch can have a hydrogen to carbon ratio ofabout of less than about 0.8, such as in ranges as less than about 0.1,less than about 0.2, about 0.1 to about 0.2, about 0.15 to about 0.25,about 0.2 to about 0.4, about 0.3 to about 0.5, about 0.4 to about 0.6,or about 0.5 to about 0.7.

In an embodiment, the pitch can be relatively free of one or moreselected impurities, such as water, non-carbon atoms including sulfur ornitrogen, or material such as coal ash or char, one or more non-carbonatoms (e.g., one or more of mercury, selenium, cadmium, arsenic, alkalimetals, oxygen, halogens, sulfur or nitrogen), or material such as coalash or char. For example, the pitch can comprise less than about 0.2 wt.% water, less than about 0.1 wt. %, less than about 0.05 wt. %, or lessthan about 0.01 wt. % water or lower. In an embodiment, the pitch caninclude one or more selected impurities in the concentrations disclosedabove.

In an embodiment, the method 100 can also include producing one or morebyproducts during block 140. Examples of the byproducts that can beformed during the block 140 are disclosed in [cited the other relatedapplications], the disclosure of each of which is incorporated herein,in its entirety, by this reference. For example, the byproducts producedduring block 140 can include at least one of one or more gases, one ormore coal liquid extract, or char. It is noted that the one or morebyproducts can also be produced during at least one of block 120 orblock 130 instead of or in addition to block 140.

The coal liquid extracts can refer to any material that is extracted orproduced from raw coal or beneficiated coal that is liquid at or nearnormal temperature and pressure (about 68° F. and 1 atmosphere ofpressure). The one or more coal liquid extracts can comprise one or moreliquid hydrocarbons. For example, coal liquid extracts can comprise oneor more of benzene, toluene, alkanes or paraffins, alkenes, C2compounds, C3 compounds, C4 compounds, T compounds, halogen compounds,phenols, or other saturated or unsaturated hydrocarbons. In someembodiments, the coal liquid extracts can include any of the impuritiesdisclosed herein at any of the concentrations disclosed herein.

Char, also known as ash, can refer to any solid material which remainsafter gases, coal extract liquids, and/or pitch have been removed fromraw coal. Char can be produced during at least one of block 120, block130, or block 140. In an example, the char can comprise a solid highsurface area carbonaceous material. In an example, the char can have arelatively low hydrogen to carbon ratio, such as a hydrogen to carbonratio that is lower than the hydrogen to carbon ratio of pitch producedat block 140. In some cases, char can have a hydrogen to carbon ratio offrom about 0.05 to about 0.65. In an example, char can additionallycomprise at least some pitch material, which can be referred to hereinas intrinsic binder impregnation. In some cases, any residual pitch orother gaseous or liquid materials can be removed from the char prior toany subsequent processing of the char.

In some embodiments, the char can include any of the impuritiesdisclosed herein at any of the concentrations disclosed herein. In someembodiments, the char can have a hydrogen to carbon ratio of less thanabout 0.7, such as in ranges as less than about 0.1, less than about0.2, about 0.1 to about 0.2, about 0.15 to about 0.25, about 0.2 toabout 0.4, about 0.3 to about 0.5, about 0.4 to about 0.6, or about 0.5to about 0.7.

The gases can comprise hydrogen and/or carbon. For example, the gasescan include H₂, CO₂, CO, CH₄, C₂H₄, C₃H₆, and/or other hydrocarbongases. The gases can also include sulfur. In some cases, these gases canbe at least one of captured, otherwise contained, or used during theprocesses described herein. In some embodiments at least 50%, at least75%, at least 90%, 95%, or 99% of any gaseous or volatile byproducts ofthe method 100 can be captured. The gases captured during certainprocess steps can be used in subsequent process steps as describedherein. In some cases, gases produced by and a captured as part of theprocesses described herein can be utilized by these same or subsequentprocesses in order to increase the efficiency and/or cost effectivenessof said processes. In some cases, the capture and reuse of byproductscan improve the efficiency and/or lower the cost of the method 100.

In an embodiment, the method 100 can include reacting captured hydrogengas (H₂) with captured carbon dioxide (CO₂) (i.e., syngas) to formmethane or another suitable gas or liquid thereby reducing the carbonfootprint of the method 100. The captured hydrogen and carbon dioxidegas can be processed chemically (e.g., catalytically) to form monomericcompounds (e.g., olefins such as ethylene and/or propylene) that canthen be polymerized into higher molecular weight resin compounds. In anexample, reacting the hydrogen with the carbon dioxide can reduce theamount of carbon dioxide produced by the method 100 by about 1% to about99%, such as by about 1% to about 25%, about 20% to about 40%, or about25% to about 50%.

In an embodiment, the pitch and the byproducts are all produced at block140. In an embodiment, at least one of the pitch and at least one of thebyproducts can be produced at separate times or separate processingsteps from one another. In an embodiment, the pitch and at least one ofthe byproducts are produced together by the process 100 and, inparticular, during block 140. In such an embodiment, the method 100 caninclude separating these products before any further processing of eachindividual product can occur. For example, pitch and coal liquidextracts can be simultaneously produced as a result of block 130 and canneed to be separated from one another, by any process now know or whichcan be developed in the future, before further processing of eitherpitch or coal liquid extracts occurs.

In an embodiment, the pitch produced during block 140 are not subjectedto further processing or refinement to alter the chemical composition ofthe pitch before block 150. In an embodiment, the pitch produced duringblock 140 can be subjected to one or more processes which can alter thechemical composition thereof prior to block 150. In an example,undesired impurities that remain in the pitch after block 140 can beremoved therefrom prior to block 150. In such an example, theundesirable impurities can include impurities that could not be removedduring block 120 and block 130 or excessive amounts of at least oneimpurity that is selected to be present in the carbon fiber. In anexample, the pitch can be subjected to one or more processes to increaseor decrease the hydrogen to carbon ratio of the pitch. In an example,the pitch can be subjected to one or more processes to produce mesophasepitch or otherwise alter the composition or properties of the pitch. Inan embodiment, the one or more byproducts can also be used to form thecarbon fiber during block 150. In such an embodiment, the one or morebyproducts can or may not be subjected to further processing orrefinement to alter the chemical composition thereof before block 150using any of the processes disclosed herein or any other suitableprocess.

At block 150, at least the pitch produced at block 140 can be treatedvia the processing facility to produce at least one of the carbon fibersdisclosed herein. In an embodiment, the pitch can be treated to productat least one of the carbon fibers disclosed herein by spinning the pitchto form carbon fibers. In some cases, spinning the pitch to form carbonfibers can include any process known in the art or developed in thefuture to convert pitch to carbon fibers, or carbon filament. In somecases, the pitch can be heated to a desired temperature during thespinning process, such as to about 650° F. In some cases, forming thecarbon fibers can comprise drawing, spinning, and heating the pitch toproduce the carbon fibers. In some cases, forming the carbon fibers cancomprise spinning filaments of the pitch, heating the pitch in air to afirst temperature, and then heating the spun pitch in an inertatmosphere to a second, higher temperature to form carbon filament. Insome cases, a plasticizer can be added to the pitch to aid in spinningthe pitch, however in some other embodiments, plasticizer may not beadded before spinning the pitch. In some embodiments, forming the carbonfibers can comprise treating the pitch to produce one or more of any ofthe advanced carbon materials described herein.

In an embodiment, block 150 can include adding one or more additives tothe pitch or the carbon fiber if the pitch has already been treated toform the carbon fiber.

The carbon fibers formed during block 150 can include one or moreimpurities therein. The properties of the carbon fibers can depend, atleast in part, on the one or more impurities that are present in thecarbon fiber. In other words, the properties of the carbon fibers can betunable via at least one of the addition, control, or removal of theimpurities from the coal. For example, the properties of the carbonfibers that can depend on the presences of the one or more impuritiescan include at least one of elasticity (Young's modulus), tensilestrength, failure mechanism, and the like. In an embodiment, the one ormore impurities can include at least one impurity that was initiallypresent in the raw coal thereby negating the need to add the at leastone impurity into at least one of the raw coal, the beneficiated coal,the pitch, or the byproducts. In an embodiment, the one or moreimpurities can include at least one impurity that was added to at leastone of the raw coal, the beneficiated coal, the pitch, or thebyproducts.

In some embodiments, where the additional advanced carbon materials cancomprise carbon fibers, the carbon fibers can have different or improvedphysical properties as compared to carbon fibers formed by conventionalprocesses (e.g., carbon fibers produced by spinning polyacrylonitrile(“PAN”)). The different or improved physical properties can be caused bythe impurities that are present in the raw coal and that remain in thecarbon fibers. In some cases, carbon fibers produced by the processesdescribed herein can have a higher degree of molecular orientation alongthe fiber axis than carbon fibers produced from PAN. In some cases,carbon fibers produced by the processes described herein can have ahigher elastic modulus than carbon fibers produced from PAN. In somecases, carbon fibers produced by the processes described herein can havea higher thermal and electrical conductivity than carbon fibers producedfrom PAN. However, in some embodiments, the additional advanced carbonmaterials can comprise PAN, and thus carbon fibers can be produced fromPAN that is formed from coal according to the processes describedherein.

In an embodiment, the carbon fibers can include any of the impuritiesdisclosed herein at any of the concentrations disclosed herein.

In an embodiment, the hydrogen to carbon ratio of the resin can be about0.7 to about 1.0, such as in ranges of about 0.7 to about 0.75, about0.725 to about 0.0775, about 0.75 to about 0.8, about 0.0775 to about0.85, about 0.8 to about 0.9, about 0.85 to about 0.95, or about 0.9 toabout 1.0.

In an embodiment, the method 100 can include recycling carbon material(e.g., resin, pitch, etc.) exhibiting a hydrogen to carbon ratio that isgreater than the desired hydrogen to carbon ratio, such as greater thanabout 0.2, greater than about 0.3, greater than about 0.4, greater thanabout 0.5, greater than about 0.6, or greater than about 0.7. Forexample, recycling the carbon material exhibiting a high hydrogen tocarbon ratio can include adding the carbon material to the raw coal, thebeneficiated coal, the pyrolyzed coal, the pitch before the pitch isprocessed, etc. Recycling the carbon material can increase the amount ofresin or other advanced carbon material that is produced during themethod 100.

As previously discussed, the beneficiated coal can be processed using adirect liquefaction process other than a pyrolysis process. The directliquefaction process can include producing resins from coal underhydrogenation conditions to produce a naphtha which can further be“steam cracked” (e.g., converted into so-called “naphtha cracker”) toproduce light olefin products (e.g., ethylene and/or) propylene. Oneexample of a direct liquefaction process includes the H-Coal processdeveloped in the Catlettsburg refinery and by Shenhua of China toproduce liquid transportation fuels, chemical intermediates, andnaphtha.

FIG. 2 is a flow chart of an example method 200 to form carbon fibersusing a direct liquefaction process, according to an embodiment. Exceptas otherwise disclosed herein, the method 200 is the same orsubstantially similar to the method 100. The method 200 can includeproviding coal to a processing facility at block 210. The method 200 canalso include beneficiating the coal via the processing facility at block220 to remove a desired amount of water, metals, and/or other impuritiesfrom the coal. The method 200 can further includes subjecting at leastsome of the beneficiated coal to a direct liquefaction process at theprocessing facility at block 230. Additionally, the method 200 caninclude producing pitch at block 240. Also, the method 200 can includemodifying the pitch to produce carbon fibers at block 250. The method200 is only an example. As such, one or more blocks of the method 200can be omitted, supplemented, combined, or divided. Further, the method200 can include one or more additional acts.

Block 230 includes processing the beneficiated coal using a directliquefaction process. The direct liquefaction process can includeheating the beneficiated coal above a desired temperature (e.g., about400° C. to about 500° C.) for a duration thereby converting thebeneficiated coal into a liquid. In some cases, the beneficiated coalcan be heated in the presence of one or more catalysts and/or at anelevated pressure. In some cases, the beneficiated coal can be heated inan atmosphere comprising H₂. In some cases, the direct liquefactionprocess can be a hydrogenation or hydro-cracking process. In such cases,the direct liquefaction process can be performed in a hydrogenatmosphere. In some cases, a solvent can be added to the beneficiatedcoal during the direct liquefaction process. In some cases, thebeneficiated coal can be subjected to a direct liquefaction processdeveloped by Axens as described, for example, in U.S. Patent PublicationNo. 2017/0313886, which is hereby incorporated by reference in itsentirety.

As previously discussed, the beneficiated coal can be processed using anindirect liquefaction process other than a pyrolysis process. Theindirect liquefaction process can include producing resins from the rawcoal in a high temperature gasification process to form so-called syngas(e.g., a mixture of hydrogen gas and at least one of carbon monoxide orcarbon dioxide). The syngas can be processed chemically to formmonomeric compounds that can then be polymerized into higher molecularweight resin compounds. For example, syngas can be converted intomethanol which can be catalytically converted into light olefins (e.g.,ethylene and/or propylene). Ethylene and/or propylene can be convertedinto carbon fibers. The light olefins formed during the indirectliquefaction process and/or the other process disclosed herein can alsobe precursors to other polymeric compounds. For example, theammoxidation of propylene results in the formation of acrylonitrilemonomers which can then be converted into polyacrylonitrile.

FIG. 3 is a flow chart of an example method 300 to form carbon fibersusing an indirect liquefaction process, according to an embodiment.Except as otherwise disclosed herein, the method 300 is the same orsubstantially similar to the method 100 and/or method 200. The method300 can include providing coal to a processing facility at block 310.The method 300 can also include beneficiating the coal via theprocessing facility at block 320 to remove a desired amount of water,metals, and/or other impurities from the coal. The method 300 canfurther includes subjecting at least some of the beneficiated coal to anindirect liquefaction process at the processing facility at block 330.Additionally, the method 300 can include producing syngas or anothercoa-derived element (e.g., char, pitch, etc.) at block 340. Also, themethod 300 can include modifying the pitch to produce carbon fibers atblock 350. The method 300 is only an example. As such, one or moreblocks of the method 300 can be omitted, supplemented, combined, ordivided. Further, the method 300 can include one or more additionalacts.

Block 330 includes processing the beneficiated coal using an indirectliquefaction process. The indirect liquefaction process can includeconverting the beneficiated coal to a gas or gases and then convertingthe gas or gases into one or more liquids. The one or more gases caninclude, but are not limited to, syngas (e.g., a mixture of H₂ and COgas). In an example, the indirect liquefaction process can includeheating the beneficiated coal to a desired temperature (e.g., about1400° C. to about 1600° C.) for a desired duration at a desire pressure(e.g., about 40 bars to about 60 bars). In an example, the gases formedduring the indirect liquefaction process can then be converted toliquids or other materials, such as ammonia or methanol. The gasesformed during the indirect liquefaction process can be converted intoliquids or other materials at a desired temperature (e.g., about 200° C.to about 350° C.) and at a desired pressure (e.g., about 10 bars toabout 40 bars). The liquids or other material can then be subjected tofurther processing to produce hydrocarbons that can be formed into thecarbon fibers, polymers that can be formed into the carbon fibers, otherprecursors of the carbon fibers, or the carbon fibers themselves. Thehydrocarbon can include olefins (e.g., ethylene and propylene), aromatichydrocarbons, toluene, benzene, paraxylene, or other hydrocarbons. In aparticular example, the gases can be converted to olefins by a processdeveloped by Honeywell UOP as described, for example, in U.S. PatentPublication No. 2015/0141726, which is hereby incorporated by referencein its entirety. In some cases, the beneficiated coal can be subjectedto an indirect liquefaction process.

As previously discussed, the beneficiated coal can be processed usingmembranes instead of a pyrolysis process. Examples of using membranes toprocess coal include separating hydrogen from coal in gasificationreactors using membranes. The membranes can include specialty ceramicmaterials, such as one or more advanced carbon-based materials (e.g.,one or more graphene-based materials). The membranes can facilitate theseparation of hydrogen from coal at relative low temperature and/orprocessing of slurry-based coal, both of which can decrease costs andimprove the efficiency of the process of formin the one or more resins.Examples of using membranes to process the beneficiated coal aredisclosed in V. Kyriakou, et al., A protonic ceramic membrane reactorfor the production of hydrogen from coal steam gasification, 553 J.Membrane Sci. 163 (2018) and Francis C. Arrillaga, et al., Coal toHydrogen: A Novel Membrane Reactor for Direct Extraction, GCEP EnergyWorkshops (2004), the disclosures of each of which are incorporatedherein, in its entirety, by this reference.

FIG. 4 is a flow chart of an example method 400 to form carbon fibersusing one or more membranes, according to an embodiment. Except asotherwise disclosed herein, the method 400 is the same as orsubstantially similar to the method 100, method 200, and/or the method300. The method 400 can include providing coal to a processing facilityat block 410. The method 400 can also include beneficiating the coal viathe processing facility at block 420 to remove a desired amount ofwater, metals, and/or other impurities from the coal. The method 400 canfurther includes processing at least some of the beneficiated coal withone or more membranes at the processing facility at block 430.Additionally, the method 400 can include producing pitch at block 440.Also, the method 400 can include modifying the pitch to produce carbonfibers at block 450. The method 400 is only an example. As such, one ormore blocks of the method 400 can be omitted, supplemented, combined, ordivided. Further, the method 400 can include one or more additionalacts.

Block 430 includes processing the beneficiated coal in the presence ofone or more membranes. In some cases, these membranes can serve to atleast one of physically separate, chemically separate, or crack thebeneficiated coal to produce products therefrom. Examples of themembranes includes advanced carbon-based materials. In an embodiment,these products can be substantially similar to the products produced bythe other liquefaction processes disclosed herein, but may not use theamount of heat or pressure that the other liquefaction process canrequire. Thus, processing beneficiated coal with one or more membranescan produce substantially similar products to a liquefaction process butcan require substantially less energy to do so. In an embodiment, theone or more membranes can comprise various pore sizes, chemicalproperties, physical properties, or electrical properties to isolatedesirable compounds and/or produce desirable compounds from thebeneficiated coal.

The beneficiated coal can be processed using other process other than orin addition to the pyrolysis processes disclosed herein, the directliquefaction processes disclosed herein, the indirect liquefactionprocesses disclosed herein, or the process disclosed herein that usemembranes. In an example, the beneficiated coal can be processed usingan electric arc process. In an example, the beneficiate coal can beprocessed using a super critical solvent extraction process. Examples ofsuper critical solvent extraction processes that can be used to processthe beneficiate coal are disclosed in Jonathan J. Kolak, A Procedure forthe Supercritical Fluid Extraction of Coal Samples, with SubsequentAnalysis of Extracted Hydrocarbon, USGS (2006) and Ye Sun et al.,Evaluation of Coal Extraction with Supercritical CarbonDioxide/1-Methyl-2-pyrrolidone Mixed Solvent

FIG. 5 illustrates a material flow diagram of an example of a method 500of producing carbon fiber and, optionally, one or more advanced carbonmaterials from coal in accordance with the present disclosure, accordingto an embodiment. Except as otherwise disclosed herein, the method 500is the same as or substantially similar to any of the methods 100, 200,300, or 400 of FIGS. 1-4. For example, the method 500 can be acombination of two or more of the methods 100, 200, 300, or 400 of FIGS.1-4. At block 510, raw coal is provided to a processing facility, forexample by a mining process, such as high wall mining. The raw coal caninclude any of the raw coal disclosed herein. The raw coal can then besubjected to a beneficiation process to remove a desired amount ofwater, metals, volatile matter, and other impurities as described hereinat block 520. The beneficiation process can include any of thebeneficiation processes disclosed herein. In some cases, thebeneficiation process can produce byproducts, such as char (block 542)and gases and/or coal liquid extracts (546), in addition to thebeneficiated coal. The beneficiated coal can be subjected to a liquidextraction process (e.g., pyrolysis, direct liquefaction, or indirectliquefaction process) at block 530 and as described herein to producepitch (block 540). Again, in some cases, the pyrolysis or liquefactionprocess of block 540 can produce byproducts, such as char (block 542)and coal liquid extracts and gases (block 546). In some cases, the char542 can be processed or treated at block 560 to produce an additionaladvanced carbon material, for example activated carbon (block 544), asdescribed herein. In some cases, the coal liquid extract 546 can beprocessed or treated at block 570 to produce at least one ofhydrocarbons (e.g., benzene and paraxylenes), carbon fibers, or otheradditional advanced carbon materials (block 548), as described herein.At block 550, the pitch can be processed or treated to produce carbonfibers (block 580), as described herein. In an embodiment, the block 580can also include processing or treating the pitch to produce one or moreadditional advanced carbon materials in addition to the carbon fiber, asdescribed herein.

In some embodiments, the method 500 can be entirely carried out at asingle processing facility. However, in some other cases, one or moreblocks can be carried out at different processing facilities and/ordifferent locations. For example, char 542 or coal liquid extract 546can be transported to a second location where blocks 560 and 570 can becarried out.

Although the processes described herein relate to the production ofcarbon-based carbon fibers and additional advanced carbon materials fromcoal, in some embodiments these processes can be utilized to producesilicon products, such as silicone carbon fibers. For example, in someembodiments, sand or other raw materials comprising silicon can be usedin the processes and methods described herein to produce one or moresilicone carbon fibers.

FIG. 6 is a diagram illustrating the flow of energy and coal in aprocessing facility for the production of one or more advanced carbonmaterials as described herein and according to some embodiments. As canbe seen in FIG. 6, and as described herein, raw coal from a mine, suchas the Brook Mine in Wyoming, can be processed to form carbon fiber and,optionally, one or more additional advanced carbon materials, such asconstruction materials, and/or activated carbon.

FIG. 7 is a diagram illustrating the process flow of raw coal, forexample from a high wall coal mine, as it is processed according to theembodiments described herein to form various advanced carbon materials,such as activated carbon, graphene, materials for use in batteries, andbuilding and construction materials, according to an embodiment. Asillustrated, and according to some embodiments, processing of the coalcan produce advanced carbon materials which can themselves be subjectedto further processing to form other advanced carbon materials. Further,in some embodiments, the byproducts from the production of advancedcarbon materials can themselves be subjected to further processing toproduce other advanced carbon materials as described herein.

FIG. 8 is a diagram illustrating the process flow of raw coal to variousadvanced carbon materials according to the processes described herein,according to an embodiment. FIG. 8 further illustrates how, according tosome embodiments, the advanced carbon material produced according to theprocesses described herein can be utilized as one or more components inhigh-value finished products, such as automotive grade CFRP, or graphenebased biosensors.

Applications of the Carbon Fibers

The carbon fibers produced during at least one of the methods 100, 200,300, 400, or 500 can be configured to be used in a variety ofapplications and, optionally, these methods can include using the carbonfibers in one or more of these application. In an embodiment, the carbonfibers can be configured to be used in a carbon fiber reinforcedcomposite. For example, the carbon fibers can be combined with at leastone matrix material to form the carbon fiber reinforced composite by anyprocess known in the art or that can be developed in the future. Thematrix material can comprise at least one of a polymer (e.g., a resinmade from coal), a metal, or a ceramic material. In some cases, thematrix can include any one of the additional advanced carbon materialsdisclosed herein. In some embodiments, the carbon fiber reinforcedpolymer can be formed into a desired structure. In some embodiments, theadditional advanced carbon materials can be produced via the processesdescribed herein and can be combined with one or more other materialsvia the processing facility to produce a composite material having adesired form.

In some embodiments, the carbon fiber reinforced composite can includemetals or concrete including carbon fibers. In some examples, the carbonfiber reinforced composite can be 3D printed. In some examples, carbonfiber or the carbon fiber reinforced composites produced from coal asdescribed herein can be used as rebar in concrete or can be used asother construction materials.

In an embodiment, the carbon fibers disclosed herein can be modified onsite by a user in order to achieve the desired chemical or mechanicalproperties of the carbon fiber reinforced composite. In some cases, afirst carbon fiber produced from coal by the processes described hereincan be mixed with predetermined amount of a second carbon fiber that isdifferent than the first carbon fibers. In an example, the first carbonfiber and the second carbon fibers are both formed from coal but exhibitdifferent properties (e.g., the first and second carbon fibers includedifferent impurities). In an example, the first carbon fiber is formedfrom coal while the second carbon fibers are formed from oil. The amountof the first and second carbon fibers can be selected based on thedesired properties of the carbon fiber reinforced composite formed fromthe first and second carbon fibers. For example, where a user desires ahigher young's modulus, they can be directed to add a predeterminedamount of a first carbon fiber produced from coal in order to raise theyoung's modulus of the second carbon fiber formed from oil.

In some cases, an advanced carbon material such as carbon fibers,include activated carbon and/or can be functionalized and tuned asdesired. In some cases, any of the advanced carbon materials or carbonfibers described herein can be functionalized or used to formfunctionalized products. For example, in some cases an advanced carbonmaterial produced according to the methods described herein can befunctionalized to adsorb one or more predetermined materials, elements,and/or substances from water, the atmosphere, or other mediums asdesired. In some cases, advanced carbon material produced according tothe methods described herein can adsorb one or more types of rare earthelements produced by coal processing plants, such as the processingfacilities described herein. In some cases, advanced carbon materialproduced according to the methods described herein can adsorb one ormore valuable predetermined elements or compounds from sea water. Insome cases, advanced carbon material produced according to the methodsdescribed herein can adsorb CO₂ from the ambient atmosphere.

Additional Advanced Carbon Materials

As previously discussed, the methods and processes described herein canbe used to produce carbon fiber and, optionally, one or more additionaladvanced carbon materials from coal. As used herein, the term additionaladvanced carbon materials can refer to one or more non-carbon fibermaterials comprising carbon. The additional advanced carbon materialscan be formed from at least one of the pitch (e.g., the portions of thepitch not used to form the carbon fiber) or one or more of thebyproducts produced during the methods disclosed herein. In an example,the methods disclosed herein can be utilized to produce an amount of acarbon fiber and, subsequently, an amount of at least one additionaladvanced carbon material. In an example, the method 100 can be utilizedto produce an amount of the carbon fiber and an amount of the at leastone second advanced carbon material simultaneously, for instance, viaparallel processing utilizing the methods disclosed herein. In someembodiments, the additional advanced carbon materials can be a resin,polymer, or other hydrocarbon material.

In an embodiment, the methods disclosed herein can include forming resinfrom the pitch or byproducts produced during the methods disclosedherein. For example, the resins formed from at least the pitch caninclude polyacrylonitrile, polyurethane resins, cyanate ester resins,epoxy resins, methacrylate resins, polyester resins, fused aromatic ringstructures (e.g., polycyclic aromatic hydrocarbons), and other suitableresins. In an example, the resins formed according to the processesdisclosed herein can include resins formed from resin precursors.Examples of resin precursors include C2 compounds (e.g., ethane,ethylene, acetylene, etc.), C3 compounds (e.g., propylene, cyclopropane,propene, etc.), C4 compounds (e.g., butadiene, butane, t-butanol, etc.),benzene compounds, toluene compounds, halogen compounds, phenols, or anyother suitable resin precursor.

In an embodiment, the pitch can be treated to product at least one ofthe resins disclosed, for example, by forming the pitch into one or moreorganic compounds (e.g., olefins, other resin precursors, otherpolymers) and polymerizing the one or more organic compounds. In anembodiment, the coal liquid extracts can be treated at the processingfacility to form at least one of the resins disclosed herein. In anembodiment, forming the resins disclosed herein can include adding oneor more additives to the pitch, the byproducts, or the resin if theresin has already been formed. The additives added to the pitch,byproducts, or the resin can include one or more photo activators (e.g.,one or more ultraviolet light activates) or one or more thermalactivators.

In such an embodiment, the resin can be subjected to further processingvia the processing facility to produce a polymer part or product. Forexample, the resin can be used to produce sheets, extrusion, threedimensional structures using a molding process, or another othersuitable process. In an embodiment, the resins can be configured toproduce carbon three dimensional (“3D”) devices, such as via a 3Dprinting process. The 3D printing process can include forming the resininto meshes, hollow objects, solid objects, or other products. In someembodiments, a resin produced by the 3D printing processes describedherein can be used in a continuous liquid interface production (CLIP)process as developed by Carbon3D, Inc. In an embodiments, the materialproperties of a 3D printed objected can be varied throughout the volumeof the object by utilizing two or more resins produced form coalaccording to the processes described herein, where each of the two ormore resins has different material properties when cured and/or each isactivated by a different stimuluses. In an embodiment, the resins can beconfigured to be used in an additive manufacturing process.

In an embodiment, the methods disclosed herein can include processing atleast one of the pitch or one or more of the byproducts to formsynthetic graphite. In some cases, the synthetic graphite can besubjected to further processing to form synthetic graphene. For example,at least one of the pitch or one or more of the byproducts can betreated by exposure to heat, elevated pressure, and/or one or morecatalysts to form synthetic graphite. As used herein, the term syntheticgraphite is used to refer to any graphite material produced from aprecursor material (e.g., any graphite material that does not occurnaturally in the earth). In an embodiment, the methods disclosed hereincan further comprise treating or processing the synthetic graphite, viathe processing facility, to form synthetic graphene. As used herein,synthetic graphene refers to any graphene material produced or derivedfrom synthetically formed graphite. For example, the synthetic graphitecan be subjected to mechanical exfoliation to produce syntheticgraphene. As described herein, a desired amount of one or moreimpurities can remain in the beneficiated coal and can thereby beincorporated into the synthetic graphene produced in order to adjust thechemical, electrical, and/or physical properties of the syntheticgraphene.

In an embodiment, the methods disclosed herein can include subjectingany char produced during the methods to further processing to produceone or more additional advanced carbon material, such as activatedcarbon. In an example, processing the char can include carbonizing orheating the char (e.g., in a kiln). The char can then be activated via aphysical activation process or a chemical activation process. Physicalactivation can comprise heating the char in an atmosphere comprisingargon and/or nitrogen, or heating the char in an oxidizing atmosphere.Chemical activation can comprise impregnating the char with one or morechemicals, such as an acid, a base, or a salt. In some cases, chemicalactivation can further comprise carbonizing or heating the impregnatedchar to activate it. In some cases, chemical activation can requirelower temperatures and less energy than physical activation. Further, insome cases, chemical byproducts produced by the method 100 can beutilized during the chemical activation process.

In some cases, the additional advanced carbon materials can compriseprimarily carbon atoms. In some embodiments, the additional advancedcarbon materials can comprise at least one carbon foams, or pyrolyzedcarbon. In some embodiments, the additional advanced carbon materialscan comprise one or more allotropes of carbon, such as any allotropes ofcarbon that are known in the art or that can be developed in the future.In some cases, the additional advanced carbon materials can comprisesingle-walled carbon nanotubes, multi-walled carbon nanotubes, carbonmegatubes, carbon nanoribbons, carbon nanobuds, graphene, graphitenano-platelets, quantum dots, and fullerenes (e.g., buckminsterfullereneor multi-cored fullerenes).

In some cases, the additional advanced carbon materials can compriseelements in addition to carbon and can be, for example, a polymer orother hydrocarbon material. For example, the additional advanced carbonmaterials can comprise thermoset or thermoplastic polymers. In somecases, the additional advanced carbon materials can comprise apolyester, vinyl ester, or nylon polymer.

In some cases, the additional advanced carbon materials can comprise abiologically useful material or biopolymer. In other words, theadditional advanced carbon materials can comprise a material includingcarbon that is at least one of used in biological systems or organisms,biocompatible, or is typically be produced by a biological organism. Forexample, the additional advanced carbon materials can be a protein,amino acid, nucleic acid, collagen, chitosan, sugar, or other biologicalmaterial. In some cases, the additional advanced carbon materials cancomprise a porous material, such as a membrane, for use in a biologicaland/or chemical process. For example, the additional advanced carbonmaterials can comprise perforated graphene.

Applications of the Additional Advanced Carbon Materials

The additional advanced carbon materials produced via the methods andprocesses described herein can be used in a wide variety ofapplications. In some cases, the additional advanced carbon materialsproduced via the processing facility described herein can be subjectedto further processing to produce objects, devices, and other productsfrom the additional advanced carbon materials. In other embodiments, theadditional advanced carbon materials can be distributed to otherproduction facilities for use. Importantly, in some embodiments, theprocesses described herein can produce two or more types of additionaladvanced carbon materials which can be combined at the processingfacility into further products.

In such an embodiment, the resin can be subjected to further processingvia the processing facility to produce a polymer part or product. Forexample, the resin can be used to produce sheets, extrusion, threedimensional structures using a molding process, or another othersuitable process. In an embodiment, the resins can be configured toproduce carbon three dimensional (“3D”) devices, such as via a 3Dprinting process. The 3D printing process can include forming the resininto meshes, hollow objects, solid objects, or other products. In someembodiments, a resin produced by the 3D printing processes describedherein can be used in a continuous liquid interface production (CLIP)process as developed by Carbon3D, Inc. In an embodiments, the materialproperties of a 3D printed objected can be varied throughout the volumeof the object by utilizing two or more resins produced form coalaccording to the processes described herein, where each of the two ormore resins has different material properties when cured and/or each isactivated by a different stimuluses. In an embodiment, the resins can beconfigured to be used in an additive manufacturing process.

In some embodiments, a first additional advanced carbon materialproduced by the processes described herein can be used in a subsequentsuch process to produce a second, different additional advanced carbonmaterial. For example, the first additional advanced carbon material cancomprise molecular graphene membranes. The molecular graphene membranescan then be used in the processes described herein to chemicallyseparate products of pyrolysis or liquefaction processes to producecarbon fibers. In some cases, this form of chemical separation viagraphene membranes can be more thermally efficient than other separationprocesses that are typically employed. These carbon fibers in turn canbe used in the CLIP process, for example to print a mesh.

In some embodiments where the additional advanced carbon materialscomprise graphene, the graphene can be subjected to further treatmentvia the processing facility to form, for example, a graphene sensor.These graphene sensors can be used as disposable chips for detectingdiseases via a handheld device. The graphene sensor can be able toimmediately detect diseases, such as Lyme disease or the zika virus froma patient's blood, urine, saliva, or other bodily fluids or biologicalmaterial, thereby eliminating any need to store blood samples fortransportation to a lab. Further, the processes described herein canalso be used to print the body of the hand-held device, and/or aconsumable or attachment, such as a microfluidic chamber, for examplevia the CLIP process.

In some embodiments, additional advanced carbon materials produced bythe processes described herein can be used in a wide variety of otherapplications. For example, the additional advanced carbon materials cancomprise a carbon foam which can be used as an electrode in a lithiumion battery. In some cases, the additional advanced carbon materials cancomprise activated carbon that can be used in an atmospheric CO₂recapture process. In some cases, the atmospheric CO₂ recapture processcan be carried out via the processing facility and captured CO₂ can beused in the processes described herein.

In some embodiments, additional advanced carbon materials, such asgraphene, formed according to the processes described herein can be usedto produce solar panels. In some cases these solar panels can havegreater efficiencies than other conventionally produced solar panels. Insome embodiments, additional advanced carbon materials formed accordingto the processes described herein can be used as precursors inelectrospinning processes. For example, additional advanced carbonmaterials can be used to electrospin scaffolds or other structureshaving micron level resolution. In some cases the additional advancedcarbon materials used in electrospinning can be biomaterials producedfrom coal according to the processes described herein. In someembodiments additional advanced carbon materials can be used to producegels, for example medical grade gels such as hydrogels or silicone gels.

In some embodiments, one or more additional advanced carbon materialsproduced from coal according to the processes described herein can beused as automotive grade materials in the production of cars, trucks, orother automobiles. For example, carbon fiber reinforced compositesincluding resins formed from coal can be used as automotive frames,structural components, body panels, engine blocks, and/or othercomponents. In some cases, the components can be 3D printed and can becustom designed according to a user's preferences.

In some embodiments, one or more additional advanced carbon materialsproduced from coal according to the processes described herein can beused to form products for use in chemical or biological processes, suchchromatography columns, membranes, and filters. In some cases,chromatography columns, membranes, and/or filters can be 3D printed fromone or more additional advanced carbon materials produced from coalaccording to the processes described herein. In some cases, thechromatography columns, membranes, and/or filters can be used to isolateor remove antibodies, bacteria, parasites, and/or heavy metals fromvarious solutions.

In some embodiments, one or more additional advanced carbon materialsproduced from coal according to the processes described herein can beused to form circuit boards. For example, a carbon foam produced fromcoal as described herein can be 3D printed to form a circuit board. Insome cases a carbon foam circuit board can have superior electrical andthermal properties to typical printed circuit boards. In someembodiments, one or more additional advanced carbon materials producedfrom coal according to the processes described herein can be syntheticgraphene and can be used in a variety of electronic applications, forexample in forming quantum dots and in computer chips. In some cases,graphene can be used to produce biosensors that can be capable ofisolating and/or identifying any number of biologically active moleculesor substances, such as disease biomarkers or viruses.

Unless otherwise indicated, all numbers or expressions, such as thoseexpressing dimensions, physical characteristics, etc., used in thespecification (other than the claims) are understood as modified in allinstances by the term “approximately.” At the very least, and not as anattempt to limit the application of the doctrine of equivalents to theclaims, each numerical parameter recited in the specification or claimswhich is modified by the term “approximately” should at least beconstrued in light of the number of recited significant digits and byapplying ordinary rounding techniques. Further, the terms “have,” “has,”“having,” “include,” “includes,” and “including” should be interpretedas being both open ended and closed end terms.

In addition, all ranges disclosed herein are to be understood toencompass and provide support for claims that recite any and allsubranges or any and all individual values subsumed therein. Forexample, a stated range of 1 to 10 should be considered to include andprovide support for claims that recite any and all subranges orindividual values that are between and/or inclusive of the minimum valueof 1 and the maximum value of 10; that is, all subranges beginning witha minimum value of 1 or more and ending with a maximum value of 10 orless (e.g., 5.5 to 10, 2.34 to 3.56, and so forth) or any values from 1to 10 (e.g., 3, 5.8, 9.9994, and so forth).

We claim:
 1. A method of producing carbon fiber, comprising: providingan amount of raw coal, the raw coal including one or more impuritiestherein; beneficiating the amount of raw coal by heating the raw coal inan atmosphere comprising a halogen gas to selectively remove at leastsome of the one or more impurities relative to one or more otherimpurities comprising heteroatoms to form beneficiated coal; processingthe beneficiated coal to produce an amount of pitch; and modifying atleast some of the pitch to produce the carbon fiber; wherein the carbonfiber includes a selected amount of a remainder of the one or moreimpurities that were not removed while beneficiating the amount of theraw coal, processing the beneficiated coal, and modifying at least someof the pitch.
 2. The method of claim 1, wherein beneficiating the amountof raw coal includes removing at least 75 wt. % of at least one ofmercury, arsenic, cadmium, water, or volatile compounds.
 3. The methodof claim 1, wherein processing the beneficiated coal includes pyrolyzingthe beneficiated coal.
 4. The method of claim 3, wherein pyrolyzing thebeneficiated coal includes heating the beneficiated coal to about 400°C. to about 650° C. at atmospheric pressure.
 5. The method of claim 1,wherein processing the beneficiated coal includes at least one ofsubjecting the beneficiated coal to a direct liquefaction process,subjecting the beneficiated coal to an indirect liquefaction, or usingmembranes.
 6. The method of claim 1, further comprising capturingsyngas.
 7. The method of claim 1, wherein modifying at least some of thepitch to produce the carbon fiber includes modifying some of the pitchto produce the carbon fibers and a remainder of the pitch to form one ormore additional advanced carbon materials.
 8. The method of claim 7,wherein the one or more additional advanced carbon materials includesone or more resins.
 9. The method of claim 8, wherein modifying aremainder of the pitch to form one or more additional advanced carbonmaterials includes modifying the at least some of the pitch to form oneor more resin precursors.
 10. The method of claim 8, wherein the one ormore resins include at least one of polyethylene, polypropylene,polyacrylonitrile, polyurethane resins, cyanate ester resins, epoxyresins, methacrylate resins, polyester resins, or polycyclic aromatichydrocarbons.
 11. The method of claim 1, further comprising combiningthe carbon fibers with at least one matrix material to form the carbonfiber reinforced composite.
 12. The method of claim 11, wherein the atleast one matrix material includes at least one polymer.
 13. The methodof claim 11, wherein the at least one matrix material includes one ormore of at least one metal or at least one ceramic.
 14. A method ofproducing an advanced carbon material at a single processing facility,comprising: providing an amount of raw coal to the single processingfacility, the raw coal including one or more impurities therein;beneficiating the amount of raw coal by heating the raw coal in anatmosphere comprising a halogen gas at the single processing facility toselectively remove at least some of the one or more impurities relativeto one or more other desired impurities to form beneficiated coal;processing the beneficiated coal at the single processing facility toproduce an amount of pitch; and modifying at least some of the pitch atthe single processing facility to produce the one or more resins;wherein the one or more resins include a selected amount of a remainderof the one or more impurities that were not removed while beneficiatingthe amount of the raw coal, processing the beneficiated coal, andmodifying at least some of the pitch.
 15. The method of claim 1, whereinbeneficiating the amount of raw coal includes removing at least 75 wt. %of at least one of mercury, arsenic, cadmium, water, or volatilecompounds.
 16. The method of claim 1, wherein processing thebeneficiated coal include pyrolyzing the beneficiated coal at atemperature of about 400° C. to about 650° C.
 17. The method of claim 1,wherein processing the beneficiated coal includes at least one ofsubjecting the beneficiated coal to a direct liquefaction process,subjecting the beneficiated coal to an indirect liquefaction, or usingmembranes.
 18. The method of claim 1, wherein modifying at least some ofthe pitch to produce the carbon fiber includes modifying some of thepitch to produce the carbon fibers and a remainder of the pitch to formone or more resins.
 19. The method of claim 1, further comprisingcombining the carbon fibers with at least one matrix material to formthe carbon fiber reinforced composite.